Photo‐ and Redox‐Active Dendritic Molecules with Soft,Layered Nanostructures

Molecules with one photoactive group (porphyrin) and multiple redox‐active groups (ferrocenes) are described. The molecules are based on dendritic frameworks, with the ferrocenyl groups attached at the “internal” positions and the porphyrin attached at the focal point, leading to a characteristic layer architecture. Molecules of up to the third generation were synthesized and examined. The results of ¹H NMR spectroscopy and fluorescence quenching indicated that the ferrocenyl groups at the second layer approach the core porphyrin most closely, which is consistent with the results of molecular‐dynamics simulations. The electrochemistry of the molecules was also examined in detail, and a new formula is proposed for the analysis of multiple‐electron transfer in these “redox‐pool” molecules.     

Direct measurement of the end-to-end distance of individual polyfluorene polymer chains.

Wide-field imaging of individual multichromophoric molecules and successive photobleaching were used to determine, accurately, the relative position of the chromophores in such systems. First, a polyphenylene dendrimer with well-defined geometry was used to establish the accuracy in localization that can be obtained by this methodology. For a signal-to-noise ratio of 20, interchromophoric distances could be measured with 4 nm accuracy. Next, the method was used to determine the end-to-end distribution of an end-capped polyfluorene polymer. From comparison between the experimental and simulated distributions, information on the conformation of the polymer could be deduced. It was found that the polymer has a nonlinear conformation. A conjugation length of six monomer units gave the best fit of the experimental data to the proposed model.     

Trimethylsilyl ethers of amphiphilic carbosilane dendrimers of the third–fifths generations. Specific features of hydrolysis at the water-air interface

Carbosilane dendrimers from the third to fifth generation with hydroxy groups in the surface layer of the dendrimer were synthesized, as well as their analogs with latent hydroxy groups. The dendrimers differ by the density of the carbosilane core and hydrophilic shell. The amphiphilic nature of the synthesized compounds was manifested already for more hydrophobic trimethylsilyl derivatives of dendrimers. This allowed one to observe the hydrolysis of these objects during compression of their monolayers at the water surface in the Langmuir bath. The parameters of the molecular structure of the dendrimers exert a determining effect on the rate and completeness of the hydrolysis. Published in Russian in Izvestiya Akademii Nauk. Seriya Khimicheskaya, No. 11, pp. 2125–2133, November, 2007.     

Octyl‐Decorated Fréchet‐Type Dendrons: A General Motif for Visualisation of Static and Dynamic Behaviour Using Scanning Tunnelling Microscopy?

A detailed STM study of monolayers of 3,5-bis[(3,5-bisoctyloxyphenyl)methyloxy]benzaldehyde and 3,5-bis[(3,5-bisoctyloxyphenyl)methyloxy]benzyl alcohol adsorbed on graphite is presented. Very highly resolved scanning tunnelling microscopy images are observed at room temperature in air allowing the analysis of the conformation of the adsorbed molecules. These long-chain alkyl-decorated Fréchet-type dendrons are a powerful assembly motif and initially form a pattern based on trimeric units, assembled into hexagonal host structures with a pseudo-unit cell of seven molecules, one of which remains highly mobile. Over time, the supramolecular ordering changes from a trimeric into a dimeric pattern. The chirality arising from the adsorption onto a surface of the dendrons is discussed.     

Polyacrylamide gel electrophoresis separation and detection of polyamidoamine dendrimers possessing various cores and terminal groups

Detection and separation of polyamidoamine dendrimers possessing various cores and surface groups was studied by polyacrylamide gel electrophoresis. Although many dyes and staining techniques were able to detect dendrimers on polyacrylamide gels, Coomassie Blue was found to be the most sensitive and convenient. Amine and hydroxyl terminated dendrimers were best separated under acidic conditions, while dendrimers with carboxyl surfaces required alkaline buffers. Some dendrimers were very susceptible to diffusion that could occur during their separation, staining or destaining steps. In the absence of an appropriate fixation step, dendrimers could be resolved by using small pore size gels and low voltage or current. Increasing core lengths did not significantly affect migration of a given dendrimer generation but exhibited improved separation and staining characteristics. Polyacrylamide gel electrophoresis was found to be a rapid, inexpensive, and reliable procedure to characterize many different water-soluble dendritic macromolecules.     

Synthesis and characterization of dendritic multichromophores based on rylene dyes for vectorial transduction of excitation energy

The synthesis of dendritic multichromophores based on a rigid polyphenylene scaffold is presented. Different rylene chromophores are incorporated into the core, the branches, and the surface of the dendrimer. In this way, two generations of dendritic dyads consisting of a terrylenediimide core, a stiff polyphenylene scaffold, and a perylenemonoimide periphery were obtained. Furthermore, the first synthetic approach to a dendritic triad is introduced. The outer sphere of this macromolecule is formed by naphthalenemonoimide chromophores, whereas perylenemonoimide groups are located in the dendritic scaffold, and the terrylenediimide chromophore serves as a core molecule. This multichromophore absorbs over the whole range of the visible spectrum and shows well-separated absorption envelopes. In the course of dendrimer synthesis new attempts towards a straightforward functionalization strategy for rylene dyes are also presented.     

Use of Functional Dendritic Macromolecules for the Design of Metal Oxo Based Hybrid Materials

The elaboration of porous materials by using metal alkoxides (Ce(O-ⁱPr)₄, Ti(OR)₄) as inorganic precursors and acid functionalised dendrimers as organic templates is reported. Chelation by COOH groups present at the dendrimer surface was used to control the reactivity of the metal oxide precursors, creating at the same time anchoring points for the nucleation of a gel phase. The bicontinuous gels resulting after solvent evaporation present a sponge-like structure with pore size ranging from 10 to 30 nm. The effect of the metal/dendrimer ratio, the sol preparation procedure and aging conditions were studied by XRD, FTIR, TEM, SEM and BET.     

Rotational dynamics account for pH-dependent relaxivities of PAMAM dendrimeric, Gd-based potential MRI contrast agents

The EPTPA5) chelate, which ensures fast water exchange in GdIII complexes, has been coupled to three different generations (5, 7, and 9) of polyamidoamine (PAMAM) dendrimers through benzylthiourea linkages (H5EPTPA = ethylenepropylenetriamine-N,N,N',N',N'-pentaacetic acid). The proton relaxivities measured at pH 7.4 for the dendrimer complexes G5-(GdEPTPA)111, G7-(GdEPTPA)253 and G9-(GdEPTPA)1157 decrease with increasing temperature, indicating that, for the first time for dendrimers, slow water exchange does not limit relaxivity. At a given field and temperature, the relaxivity increases from G5 to G7, and then slightly decreases for G9 (r1 = 20.5, 28.3 and 27.9 mM(-1) s(-1), respectively, at 37 degrees C, 30 MHz). The relaxivities show a strong and reversible pH dependency for all three dendrimer complexes. This originates from the pH-dependent rotational dynamics of the dendrimer skeleton, which was evidenced by a combined variable-temperature and multiple-field 17O NMR and 1H relaxivity study performed at pH 6.0 and 9.9 on G5-(GdEPTPA)111. The longitudinal 17O and 1H relaxation rates of the dendrimeric complex are strongly pH-dependent, whereas they are not for the [Gd(EPTPA)(H2O)]2- monomer chelate. The longitudinal 17O and 1H relaxation rates have been analysed by the Lipari-Szabo spectral density functions and correlation times have been calculated for the global motion of the entire macromolecule (tau(gO)) and the local motion of the GdIII chelates on the surface (tau(lO)), correlated by means of an order parameter S2. The dendrimer complex G5-(GdEPTPA)111 has a considerably higher tau(gO) under acidic than under basic conditions (tau(298)gO = 4040 ps and 2950 ps, respectively), while local motions are less influenced by pH (tau(298)lO = 150 and 125 ps). The order parameter, characterizing the rigidity of the macromolecule, is also higher at pH 6.0 than at pH 9.9 (S2 = 0.43 vs 0.36, respectively). The pH dependence of the global correlation time can be related to the protonation of the tertiary amine groups in the PAMAM skeleton, which leads to an expanded and more rigid dendrimeric structure at lower pH. The increase of tau(gO) with decreasing pH is responsible for the pH dependent proton relaxivities. The water exchange rate on G5-(GdEPTPA)111(k(298)ex = 150 x 10(6) s(-1)) shows no significant pH dependency and is similar to the one measured for the monomer [Gd(EPTPA)(H2O)]2-. The proton relaxivity of G5-(GdEPTPA)111 is mainly limited by the important flexibility of the dendrimer structure, and to a small extent, by a faster than optimal water exchange rate.     

Starburst Dendrimers: Molecular-Level Control of Size,Shape, Surface Chemistry,Topology, and Flexibility from Atoms to Macroscopic Matter

Starburst dendrimers are three-dimensional, highly ordered oligomeric and polymeric compounds formed by reiterative reaction sequences starting from smaller molecules—“initiator cores” such as ammonia or pentaerythritol. Protecting group strategies are crucial in these syntheses, which proceed via discrete “Aufbau” stages referred to as generations. Critical molecular design parameters (CMDPs) such as size, shape, and surface chemistry may be controlled by the reactions and synthetic building blocks used. Starburst dendrimers can mimic certain properties of micelles and liposomes and even those of biomolecules and the still more complicated, but highly organized, building blocks of biological systems. Numerous applications of these compounds are conceivable, particularly in mimicking the functions of large biomolecules as drug carriers and immunogens. This new branch of “supramolecular chemistry” should spark new developments in both organic and macromolecular chemistry.     

FT-IRRAS spectroscopic studies of the interaction of avidin with biotinylated dendrimer surfaces

The interaction of avidin with biotin on a functional Au surface containing fourth generation amine-terminated polyamidoamine (G4-NH₂ PAMAM) dendrimers was investigated through the use of Fourier transform infrared reflection–adsorption spectroscopy (FT-IRRAS). The first step in the fabrication of the functional surfaces used was the construction of an aldehyde-terminated self-assembled monolayer (SAM) through the treatment of Au-coated glass slides with ethanol solutions of self-synthesized 2-hydroxypentamethylene sulfide (HPMS). The as-formed aldehyde-terminated monolayer was subsequently immersed in methanol solutions of G4-NH₂ PAMAM dendrimer to obtain well-organized primary amine-terminated surfaces. Biotinylation of the amine-terminated layers thus obtained was accomplished by use of the N-succinimidyl ester of biotin. Each step of the synthetic process, as well as the performance of final surface for protein recognition was monitored by FT-IRRAS. In particular, the molecular recognition ability was examined and quantified by use of an alkyne dicobalt hexacarbonyl probe coupled with avidin. Non-specific adsorption of avidin was determined by exposure of the amine-terminated and/or biotinylated surfaces to solutions of biotin-saturated avidin. The results indicate that the biotinylated G4-NH₂ PAMAM dendrimer layers formed according to this procedure have a high capacity for binding avidin with relatively high specificity. The performance of these layers (i.e. both binding capacity and specificity) improve substantially when 6-mercapto-1-hexanol (MH) is present as a co-adsorbent during the formation of the initial aldehyde-terminated layers. This effect can be attributed to the dilution of the initial aldehyde-terminated SAM, leading to a more favorable spatial arrangement of the subsequent biotinylated surfaces.